Heterocyclic bases of the aminoimidazoline series and process of preparing them



\ G-EORG KRANZLEIN AND PAULHOCHWAT, on rn mon'r on 'rnn-mAxit-nocnsr,enia MANY, ssIGNons TO I. G;FARBENINDUS'IRIEAKTIENGESELFORT-ON-THE-MAIN, GERMANY, A CORPORATION OF oaa lmny,

Patented June 6, 1933 PATENT oFnlcs,

HETEROCYCLIC BASES on THE AMINQIMIDAZOLINE snnr ns, Ann rnoonssorPREPARING THEM No Drawing. Application filed A ril 8, 1929, Serial no.353,662,.31111 in eermanyaprn 27, 1928.

The present invention relates to heterocycllc bases of theaminonnidazohne serles of the following general formula We have foundthat thebases of the amino- IIIlldtZOllllE series are easlly obtainedwlth a goodvyield by causing the ethers ofethylene thioureas toreactwith amineswith or without usinga diluent, andat a temperature ofbetween 100 C. and 200 C. The bases thus obtained are readily soluble inorganic solventswith the exceptionof ether. They dissoli e in Waterwitha stronglywalkaline re-,

action. .Thesaid. bases are intendedpto be used as intermediateproductsfor the prepa ration of dyestuffs and auxiliary means in dyeing.These compounds constitute moreover extremely valuable acceleratorswhich even with a lowcontent of sulfur yield vulcanized products whosetensile strength is by 2025 per cent higherthan usual.

- The products of the aforej-mentioned class 1 which as we havefoundconstitute new vulcan1zers,show an extremely high elliciency asaccelerators which are assuch in many cases superior for instanceto'diarylguanidine.

For example tolylaminoimidazoline is an accelerator Wl1lOl1 acts withinwide l1m1ts of temperature and yields vulcanized products.

of a high tensile strength and great elasticity.

iiWith normal vulcanization temperatures, i under to 4: atmospherespressure, the Vulcanization of the mixturesprepared with the saidaccelerator, can be" effected in a very short time. A special advantageof this product is that the vulcanizedproducts prepared l therewith arenearly odorless. By vulcanizing for instance 100 parts of rubber, 3parts of sulfur, 5 parts of zincioxide, 1 part ofpara-tolylaminoimidazolineunder 3 at mosphems Pressure t e tensilestrength ,i

with diphenylguanidine.

The following examples-serve to illustrate the invention, but they arenot intended to much superior to that of a rubber prepared.limitit'thereto, the parts being by weight:

(1) 50 parts of ethylene thiourea iodomethylate (prepared from ethylenethiourea and methyl iodide and which recrystallized. from alcoholhas amelting point of 137 C.) and 44 parts of para-toluidine are boiled" in250-parts-of amylalcohol until the develop ment of mercaptan iscomplete; the mass is then distilled with water-vapor in orderjto removetheamylalcohol and the unchanged toluidine; The remainingaqueous'solution of tolylamino-imidazoline is filtered andthe filtrateis rendered strongly alkalineby means of caustic soda solution. Theimidazoline which has separated is filteredlwith suctionfand Washedwithcold Water, This; product can be freed from any still 'adher-ffingtoluidine by washing it with ether." It crystallizes from water inlong needles having a melting pointof 133 Cr'134z9 G. The reaction maybe illustrated by the following formulae: l

The corresponding phenylamine (forming when recrystallized from water[white laminae) melts at 122 0.. The N-( phenyl- 190/ sena m nx :7

' Example 1. The reaction may be illustrated by the following formulaeIn an analogous manner ethylene thiourea can be caused to react withother amines, such as for poundsare valuable intermediate products foruse-in pharmaceutical and dyestuif chemistry and auxiliary means fordyeing purposes. V

(3) If there is used cyclohexylamine instead of the paratoluidinementioned in EX- ample 1 and the process is otherwise carried out asindicated in Example 1, cyclohexylamino-imidazoline is obtained havingits melting point at 102 C. (when crystallized from chlorobenzene). Thereaction may be illustrated by the following formulae;

instance cyclohexylaniline V naphthylamine or the like. The new comtoreact with cyclohexylamine of the formula: NH .G H at a temperaturebetween 100 C. to 200 C. in the presence of an alcohol as a diluent.

3. As a new product the compound of the formula:

forming a white crystalline body of the melting point of 133 C. to 134C. 1 1 1 .3

41. As a new product the compound of the formula:

ofthe melting point of 102 G. when crystallized from chlorobenzene.

5. The process which comprises causing a compound of the formula: I

Bio-1 1 CSa1ky1 H2C-N 1. The process which comprises causing(metl1yl.thio-) imidazoline of the formula:

'- to react with para-toluidine of the formula:

H- N.C I-LQCH at a temperature between 100 C; to 200 C. in the presenceof an alcohol as a diluent. 1

2. The process which comprises causing (methyl.tl1io-) imidazolineof theformula:

Hue-I d oscrr;

H2CN

R1 HN wherein R stands for hydrogen or alkyl, R stands for a carbocyclicaromatic radical or a carbocyclic hydroaromatic radical at a temperaturebetween 100 (l to 200 C.

6. The process which comprises causing a compound of the formula:

H EEC-fi CSalky1 H2C-N a to react with an amine of the formula:

wherein R standsfor hydrogen or alkyl, R

stands for a carbocyclic aromatic radical or a carbocyclic hydroaromatlcradicalata temcc v e wherein R stands foi -hydrogen or alkyl R standsfora carbocyclic aromatic radito react withan amine of the formula: 20 wperature between 100 Cito 200 C. the amine beingemployed in excess. a 7.The process which comprises causing acompound of the formula:

wherein R stands for hydrogen or alkyl, R; standsfor a carbocyclicaromatic radical or a carbocyclichydroaromatic radical at a tem peraturebetween 100 C. to200y C. in the presence of an alcohol as a diluent.

9. The: process which comprises causing a compound of the formula:

1 H H2C-I!I GSalkyl H2CN to react with an amine of the formula:

cal or. a carbocyclic hydroaromatic radical at a temperature between 100C. to 200 C.

in thepresence of amylalcohol as a diluent.-

100 C. to 200 C. in the alcohol asa diluent;

i 10. The process which comprises causing (methyl. thio limidazoline ofthe formula;

: H e e a I moat G SOHa HaU-N/ I to react with an amine of: the formula:

I I i i p 1 R13" wherein R stands for hydrogen or alkyl,

R stands for a carbocyclic aromatic radical .or a carbocyclichydroaromatic radical at a temperature between: 100 C. to 200 C.

in the presence of an alcohol as a diluent.

11. The process which comprises causing (methy1. thio-) imidazoline ofthe formula:

to react with an amine of the formula: H NR wherein R stands for acarbocyclic aromatic radical or a carbocyclic hydroaromatic radical at atemperature between presence of an 12. The process which comprisescausing (methyl-thio-) :imidazoline of the formula:

to react with an amine of the formula: ILNB wherein R stands foracarbocylic aromatic radical at a temperature between 100 C. to 200 (1 inthe presence of analcohol as a diluent. a e v 13. The compounds of thegeneral forlnula: H

wherein R stands for hydrogen or alkyl, R stands for a carbocyolicaromatic radical or i a carbocyclic hydroaromatio radical, saidcompounds being white crystalline products,

readily dissolving in water With an alkaline 7 reaction and having theproperty of accelerating the vulcanization of caoutchouc.

i 1 1.- The compounds of thegeneral formula:

, I y H e HzCl Q" i G-NH-Ra Inc-N V wherein R stands for: a carbocyclicaromatic radical or a carbocyclic hydroaromatic radical; said compoundsbeing White crystallin'products, readily dissolving in Water With analkaline reaction and having the property of accelerating thevulcanization of caoutchouc.

In testimony whereof, We afiix our signatures.

GEORG KRANZLE'IN. PAUL v OGHWAT.

